JPH02302408A - Catalytic component for olefin polymerization - Google Patents

Abstract

PURPOSE:To obtain the subject catalytic component providing polymers having high stereoregularity and high density by blending a solid comprising a metallic oxide, organomagnesium compound and a specific alkoxide with an olefin in the presence of an olefin, then with a specific alcohol, electron donor and Ti compound. CONSTITUTION:A metallic oxide is brought into contact with dihydrocarbylmagnesium, then with a compound shown by formula I (X<1> is H, halogen or 1 to 20C hydrocarbon; M is B, C, Al, Si or P; R<1> is 1 to 20C hydrocarbon; (m) is valence of M; (m)>(n)>=0) and a titanium alkoxide shown by formula II (R<2> is 1 to 12C hydrocarbon) to give a solid, which is brought into contact with an olefin in the presence of an organomagnesium compound, then with a halogen-containing alcohol and further with an electron donative compound and a titanium compound to give the objective catalytic component.

Description

[Detailed description of the invention] Industrial applications The present invention relates to catalyst components for olefin polymerization.

BACKGROUND OF THE INVENTION During olefin polymerization, it is important to prevent destruction of the resulting polymer, and for that purpose treatments are usually carried out to increase the strength of the catalyst particles themselves. A typical method is prepolymerization of catalyst components.

In this treatment, before the catalyst component is subjected to olefin polymerization, a small amount of olefin is polymerized in the presence of an organoaluminum compound, and the resulting polymer is incorporated into the catalyst component. However, when a so-called magnesium-supported catalyst is subjected to this prepolymerization treatment, the activity of the catalyst is significantly reduced when stored for a long period of time.

In order to suppress this catalyst deterioration, a method of washing the catalyst component after prepolymerization treatment with a large amount of organic solvent has been adopted, but the effect cannot be said to be sufficient.

On the other hand, catalysts using metal oxides such as silica as carriers are also known in order to reduce catalyst residue in polymers.
There are problems similar to those of the magnesium supported catalyst described above.

Recently, a proposal has been made to prevent deterioration of the catalyst by prepolymerizing the magnesium-containing solid before supporting the titanium component on the magnesium-containing solid (Japanese Patent Laid-Open No. 63-8
No. 9508 to No. 89511). However, the catalyst components described in these publications consist of a combination of specific compounds, and the catalyst activity itself cannot be said to be high.

Problems to be Solved by the Invention The present invention provides an olefin that has high catalytic activity, that is, has little catalyst residue in the polymer, does not deteriorate even after long-term storage, and has improved catalyst particle strength to a practical level. The object of the present invention is to provide a metal oxide-supported catalyst component for polymerization.

Means for Solving the Problems The present inventors first contacted a metal oxide, dihydrocarbylmagnesium, and a hydrocarbyloxy group-containing compound to contact a halogen-containing alcohol, and then added an electron-donating We have developed a method for producing a catalyst component for olefin polymerization, which involves bringing a compound and a titanium compound into contact with each other (Japanese Patent Application Laid-open No. 7706/1983).

Although this catalyst line segment has polymerization performance at a practical level and the particle properties of the obtained polymer are also excellent, there was a problem of storage deterioration.

The present inventors have discovered that the object of the present invention can be achieved by contacting an olefin in the presence of an organoaluminum compound after contacting with a titanium alkoxide before contacting with a halogen-containing alcohol when preparing the catalyst component. They discovered this and completed the present invention.

Summary of the Invention That is, the summary of the present invention is as follows: (a) After bringing the metal oxide and (b) dihydrocarbylmagnesium into contact, (c) general formula X', M(OR'). [However, x' is a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 20 carbon atoms; , m represents the valence of M, and m>n≧O. ] and (d) a titanium alkoxide represented by the general formula Ti(OR”)= [wherein R2 represents a hydrocarbon group having 1 to 12 carbon atoms]. in the presence of an aluminum compound, (f) contacting with an olefin, then (t) contacting with a halogen-containing alcohol, and further (th)
It is a catalyst component for olefin polymerization which is brought into contact with an electron-donating compound and a (I) hatitanium compound.

Raw materials for preparing the catalyst component (a) Metal oxide The metal oxide used in the present invention is an oxide of an element selected from the group of elements of Groups 1 to 2 of the Periodic Table of Elements,
Examples include B, 03, MgO, A1a03.
5102, Can, TI[]2, ZnO1Z
Examples include r02.5n02, Ba mouth, Th02, etc.

Among these, 83 mouths 5, MgO, ^1203.510
2, Tie, ZrO□ is desirable, especially 5ins
is desirable.

Furthermore, composite oxides containing these metal oxides, such as Si
L-MgO, 5i02-Al□Os, 5tO2T10
2, SiO, -V, mouth 3, S+02 Cr2O3,
5i02 TiO2-MgO etc. may also be used.

The above metal oxides and composite oxides are basically desirably anhydrous, but a trace amount of hydroxide, which is usually mixed, is allowed.

In addition, impurities may be mixed in to the extent that the properties of the metal oxide are not significantly impaired. Acceptable impurities include oxides such as sodium oxide, potassium oxide, lithium oxide, sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, sodium sulfate, aluminum sulfate, barium sulfate, potassium nitrate, magnesium nitrate, and aluminum nitrate; Examples include salts, sulfates, nitrates, and the like.

These metal oxides are usually in the form of powder. The size and shape of the powder often affect the shape of the obtained olefin polymer, so it is desirable to adjust it appropriately. For the purpose of removing poisonous substances before use, it is desirable to sinter metal oxides at as high a temperature as possible, and to handle them in a manner that prevents them from coming into direct contact with the atmosphere.

(l12) Dihydrocarbyl magnesium Dihydrocarbyl magnesium (hereinafter referred to as organic Mg
) is represented by the general formula RMgrR'. In the formula, R and R' are the same or different alkyl, cycloalkyl, aryl, or aralkyl groups having 1 to 20 carbon atoms.

An example of organic Mg is dimethylmagnesium (hereinafter referred to as
Magnesium is abbreviated as H8), diethyl Mg1, methyl methyl Mg1, dipropyl Mg, diisopropyl Mg1
Ethylpropyl Mg1 Dibutyl Mg1 Diisobutyl Mg
, di5ec-butyl, di-tert-butyl Mg1 butyl ethyl Mg1 butylpropyl Mg1se butyl ethyl Mg, tert-butyl isopropyl Mg, se
Kano butyl tert-butyl Mg, dibentyl Mg1 diisopentyl Mg1 ethyl pentyl! 14g1 Isopropylpentyl MgX5e Butylpentyl Mg1 Dihexyl Mg1 Ethylhexyl Mg1 Butylhexyl Mg5t
ert-butylhexyl Mg, (2-x thylbutyl)ethyl Mg, (2,2-diethylbutyl)ethyl Mg1 diheptyl Mg1 dioctyl Mg1 di2-ethylhexyl Mg1 didecyl Mg1 dicyclohexyl Mg1
Cyclohexylethyl Mg1 Butylcyclohexyl Mg
1di(methylcyclohexyl) Mg, diphenyl Mg
1-functional tylphenyl Mg1 Butylphenyl Mg5se Butylphenyl Mg1 Ditolyl Mg1 Ethyl tolyl Mg1
dixylyl Mg1 dibenzyl Mg1 benzyl tert-
Butyl Mg1 Diphenethyl Mg, Ethylphenethyl Mg
etc.

These organic Mg may be a mixture or a complex compound with an organic compound of another metal. Organic compounds of other metals have the general formula MRn (where M is boron, aluminum, aluminum, or zinc, R is an alkyl, cycloalkyl, aryl, or aralkyl group having 1 to 20 carbon atoms, and n is a metal M ). Specific examples thereof include tripel aluminum, tributyl aluminum, triisobutyl aluminum, triphenyl aluminum, triethyl boron, tributyl boron,
Diethyl beryllium, diisobutyl beryllium,
Examples include diethylzinc and dibutylzinc.

The ratio of the mixture or complex compound of organic Mg and organic compounds of other metals is usually per gram atom of magnesium,
5 gram atoms or less of other metals, preferably 2 gram atoms or less.

(c) In the compound formula of general formula X', M(OR'), M, X', R', m and n have the same meanings as above. Further, X1 may be a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms. When xl is a hydrocarbon group, xI and R' may be the same or different.

Hereinafter, the compound of the above general formula will be simply referred to as an alkoxy compound.

Hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, l-propyl, butyl, amyl, hexyl, octyl, 2-ethylhexyl, decyl, cycloalkyl groups such as cyclopentyl, cyclohexyl, methylcyclohexyl, allyl, propenyl, butenyl. Examples include alkenyl groups such as, aryl groups such as phenyl, tolyl, and xylyl, and aralkyl groups such as phenethyl and 3-phenylpropyl. Among these, alkyl groups having 1 to 10 carbon atoms are particularly desirable.

Specific examples of alkoxy compounds are listed below.

C (OCH3) contained in the compound formula C (OR'), when 0M is carbon, , C
(C, H6),.

C(DC-H=)4. C(OC4H-)-, C(0-
i-C-H-)-.

C(0(,R13)4, C(DC,)I,,),
:Formula X'C(OR'), D Contained HC(OCH3)
3, HC(DC2)+5>3, )IC(OCJ
t)s.

IC(OC4H11)'3.1lC(0-i-CJs)
1. HC(OCaHls)a.

HC(DC=)I, 7)3. HC(OCs)ls)
3' CHaC (HCl5) 3゜CH,C (mouth C-H
5)-, CJsC(OCL)a, C-)1sC
(OCaHs)s.

C,)I,, C(OC2H8)3, C5HsC
(OCH3)s, Cg)l, C(DC.

L), , C, LC(mouth CJt)s, C
J,C(DCJs)s.

cat+sc (mouth CJs)s: C) IJrC(
DC2Hs)s, CH2CIC(OC2H5)
3, CHCl2C(DCJs)s, CH3
CIC(DC2)+5)3:CIC(QC)13)
! , CIC(OC2H5)3 , CIC(
OCsLL.

CIC(0-i-CJs)+, CIC(OCaL
tL, CIC(OCIIH5)3゜BrC(OC
aHs) a 'Formula
,H,), ,C)1. (OCH,)2.

CL(OC2L)2, C)12CICH(OCJ
5)2, CHCl2C)I(DC2)1s)2
, CCI, CH(OCaHs)z, C)1.
BrcH(DCJs)z.

CH21CH(OC2H5)2, C5H5CH
(OC2H5)2.

Si(CH3)4 contained in compound formula 5i(OR')4 when 0M is silicon,
5i(OCJs)n.

Sl (DC4) 1s) 4, Sl (low 1-
CJs)n, 5i(OCaHls)s.

5i(OCJ, t)-, Sl Clow C11-CH(
CJs)C4H-)4.

5i(OCsHs)a; Formula R31(OR')a
HSI (OCJs), HSI (DC
4)111)3, HSi(OCsl(+s)a
.

HSi(OCiHs)a, CHsSi(OCH
s)s, CHsSi(mouthC2t(s)3゜C1
13Sl(OCJs)a, CzHsSi(DCs)
Is)3, CJsSi(OC2Hs)a, Cd1
sSi(OCJs)s, CJsS+(OCsHs)
s.

Cl5i(DC)13)3, Cl5i(DC2
11s)s, Cl5i(DC,H,),
.

Cl5i (mouth C, H5)3, Br5i (OCJ
s)a' (included in formula R25i(OR')z)
C)13) zsi (OCH3) 2 , (CH
s) *Si (OCJs) 2゜(CHa)isi(
OCJt)z, (CJs)2si(OCJs)
2.

'(Cs)Is)asi(DC2Hs)2,C)I
sCISi(OCJs)*.

CHCl1SiH(OCJs)z, CC1aSif
l(OCJs)a.

CHsBrSi(OCaHs)z, CHslSiH
(OCJs)a: Formula 1 Formula %) ■ B(OC,)l,) contained in compound 2B(OR'), when M is boron
, , B (DC.

H,), , B(DC,H,3)3, B(OC,
1lS)3゜■ ^1(OCL)s included in the compound formula ^1(OR')3 when M is aluminum,
AI (QC.

)1s)! , AI(OCJt)3. AI (old-C
Jt) a, Al (DC4)111)3,
AI(Ot-[:n1ls)a, AI(mouthC6
L3)3, AI(QCsH6)3.

■ When M is phosphorus, compound 2P(OR'), P(QC)13)3 contained in
, P(OC2H5)3 , P(QC-R9)3
, P(OC6H83)3, P(OCaHs)s.

(d) Titanium alkoxide Among the compounds represented by the above general formula, R
There are compounds in which 2 is an alkyl group, an aryl group, or a cycloalkyl group having 1 to 8 carbon atoms. Specific examples of R2 include methyl, ethyl, i-propyl, n-propyl, i-
Butyl, n-butyl, t-butyl, n-hexyl, n-
Examples include alkyl groups such as octyl, aryl groups such as phenyl and tolyl, and cycloalkyl groups such as cyclohexyl.

(E) Organoaluminum compound The organoaluminum compound has the general formula R,,AlX
3-. ．． (However, R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is an arbitrary number in the range of 1≦n≦3.) Alkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum civalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, dialkyl aluminum monohydride, etc. with 1 to 1 carbon atoms
Particularly preferred are alkylaluminum compounds having 8, preferably 2 to 6 carbon atoms, or mixtures or complexes thereof. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, etc. dialkylaluminum monohalides, methylaluminum dichloride, ethylaluminum cyclolide, methylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, isobutylaluminum dichloride, monoalkylaluminum cybarides, ethylaluminum sesquichloride, etc. Dialkyl aluminum monoalkoxides such as sesquihalide, dimethyl aluminum methoid, diethylaluminum ethoxide, diethylaluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum minilum hydride, dipropyl Examples include dialkyl aluminum hydrides such as aluminum hydride and diisobutyl aluminum hydride. Among these, dialkylaluminum monohalides, particularly diethylaluminum chloride and diisobutylaluminum chloride, are preferred.

Furthermore, an organic aluminum compound in which two or more pieces of aluminum are bonded via an oxygen atom or a nitrogen atom can also be used. Such compounds include, for example, (C2H5)2
AIOAl(C,H5)2.

(C4) 1! l) 2A10^1(C4H8)2,
Examples include (C2H5)2AINAI(C2H5)22H5.

(f) Olefin As the olefin, a monoolefin having 1 to 10 carbon atoms is used, and specific examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and the like.

(g) Halogen-containing alcohol The halogen-containing alcohol used in the present invention is - Any one or more hydrogen atoms other than the hydroxyl group in a mono- or polyhydric alcohol having one or more hydroxyl groups in the molecule. means a compound substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, iodine, and fluorine atoms, with chlorine atoms being preferred.

Examples of these compounds include 2-chloroethanol, 1
-chlor-2-propatol, 3-chlor-1-propatol, 1-chloro-2-methyl-2-propatol,
4-Cool-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, 3-chloro-
1,2-propanediol, 2-chlorocyclohexanol, 4-chlorobenzhydrol, (m,o,p)-
Chlorbenzyl alcohol, 4-chlorcatechol, 4
-chloro-(m,○)-cresol, 6-chloro-
(m,o)-cresol, 4-chloro-3,5-dimethylphenol, chlorohydroquinone, 2-benzyl-
4-chlorophenol, 4-chloro-1-naphthol,
(m,o,p)-chlorophenol, p-chloro-α-
Methylbenzyl alcohol, 2-chloro-4-phenylphenol, 6-chlorthymol, 4-chlorresorcin, 2-bromoethanol, 3-bromo-1-propanol, 1-bromo-2-propanol, 1-bromo- 2
-butanol, 2-bromo-p-cresol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, (
m,o,p)-bromophenol, 4-bromoresorcin, (m,o.

p)-70 lophenol, p-iodophenol = 2,
2-dichloroethanol, 2,3-dichloro-1-propatol, 1,3-dichloro-2-propatol, 3-
Chlor-1-(α-chloromethyl)-1-propatur, 2.3-dibromo-1-propatur, 1.3-sifurome-2-propatur, 2.4-dibromophenol, 2.4-dibrome -1-naphthol: 2.2.2-)
Dichloroethanol, ■, 1゜1-) dichloroethanol, β, β.

β-Trichlor-tert-butanol, 2.3°4-
Trichlorophenol, 2.4.5-) Ribromophenol, 2,4.6-)'J Chlorphenol, 2.4.
6-) Ribromophenol, 2.3.5-tribromo-
2-Hydroxytoluene, 2,3.5-)ribrome-4
-Hydroxytoluene, 2.2.2-Olifluoroethanol, α, α, α-trifluoro m-cresol,
2.4.6-Doliodophenol: 2゜3.4.6-
Ketone chlorophenol, tetrachlorohydroquinone, tetrachlorbisphenol A1 tetrabromobisphenol A12゜2.3.3-tetrafluoro-1-propatol, 2.3.5.6-ketonefluorophenol, tetrafluororesorcin, etc. It will be done.

(H) Electron-donating compounds Examples of electron-donating compounds include carboxylic acids, carboxylic anhydrides, carboxylic esters, carbonic acid halides, alcohols, ethers, ketones, amines,
Examples include amides, nitriles, aldehydes, alcoholates, phosphorus, arsenic and antimony compounds bonded to organic groups via carbon or oxygen, phorophamides, thioethers, thioesters, carbonic acid esters and the like.

Among these, carboxylic acids, carboxylic anhydrides, carboxylic esters, camafonic acid halides, alcohols, and ethers are preferably used.

Specific examples of carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, pivalic acid, acrylic acid, methacrylic acid, and crotonic acid, malonic acid, and succinic acid. acids, aliphatic dicarboxylic acids such as glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, aliphatic oxycarboxylic acids such as tartaric acid,
・Alicyclic carboxylic acids such as cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid,
Aromatic monocarboxylic acids such as anisic acid, p-tert-butylbenzoic acid, naphthoic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, Examples include aromatic polycarboxylic acids such as mellitic acid.

As the carboxylic acid anhydride, acid anhydrides of the above-mentioned carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above-mentioned carboxylic acids can be used, and specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl pivalate, isobutyl pivalate, acrylic. Ethyl acid, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, diethyl succinate, dibutyl succinate, diisobutyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate,
Diisobutyl adipate, dibutyl sebacate, diisobutyl sebacate, diethyl maleate, dibutyl maleate, diisobutyl maleate, monomethyl fumarate, diethyl fumarate, diisobutyl fumarate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate, ethyl cyclohexanecarboxylate, Methyl benzoate, dityl benzoate, methyl p-)rulyate, ethyl p-tert-butylbenzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, ethyl cinnamate, phthal Monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, diisobutyl isophthalate, diethyl terephthalate, Examples include dibutyl terephthalate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, tetramethyl pyromellitate, tetraethyl pyromellitate, and tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above-mentioned carboxylic acids can be used, and specific examples thereof include acetic acid chloride, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride, butyric acid chloride, butyric acid bromide, acetic acid iodide, and pivalin. Acid chloride, pivalic acid bromide, acrylic acid chloride, acrylic acid bromide,
Acrylic acid iodide, methacrylic acid chloride, methacrylic acid iodide, methacrylic acid iodide, crotonic acid chloride, malonic acid chloride, malonic acid promide,
Succinic acid chloride, succinic acid bromide, glutaric acid chloride, glutaric acid bromide, adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid chloride, maleic acid chloride, maleic acid chloride, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride , tartaric acid bromide, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid chloride, 1-cyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid chloride, benzoyl chloride, benzoyl bromide, p- ) toluylic acid chloride, p-toluylic acid bromide,
p-Anisyl chloride, p-anisyl bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic acid dichloride, phthalic acid dibromide, isophthalic acid dichloride, isophthalic acid dibromide, terephthalic acid dichloride, naphthalic acid Dichloride is mentioned.

Monoalkyl halides of dicarboxylic acids such as monomethyl adipate chloride, monoethyl maleate chloride, monomethyl maleate, and butyl phthalate chloride may also be used.

Alcohols are represented by the general formula ROH.

In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms.

Specific examples include methanol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol, ethylphenol, isopropylphenol, p-tert-butylphenol, n-octylphenol, and the like. Ethers have the general formula ROR
' In the formula, R and R' have 1 to 12 carbon atoms.
alkyl, alkenyl, cycloalkyl, aryl, aralkyl, and R and R' may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, ethylphenyl ether, and the like. Also, any of the halogen-containing alcohols mentioned above may be used.

(S) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, and examples include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxytitanium. , dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride, and the like. Among these, tetravalent titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

Preparation method of catalyst component The catalyst component of the present invention is prepared by contacting a metal oxide with 4g of organic N, then contacting the alkoxy compound and titanium alkoxide, and contacting the resulting solid with an olefin in the presence of an organoaluminum compound. and then contact with a halogen-containing alcohol and further contact with an electron donating compound and a titanium compound.

(1) Contact between metal oxide and organic Mg Metal oxide (A
Component) and organic Mg (component B) are brought into contact by a method of mixing and stirring in the presence or absence of an inert medium, a method of mechanical co-pulverization, and the like. Inert media include hydrocarbons such as pentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, 1,2-dichloroethane, 1,2-cyclopropane,
Halogenated hydrocarbons such as carbon tetrachloride, butyl chloride, isoamyl chloride, bromobenzene, chlorotoluene, etc. can be used.

At? , the contact between component B and B is usually between -20°C and +150°C.
℃ for 0.1 to 100 hours. The contact ratio of component A and component B is B/A=0.01 to 10 in molar ratio. Both contact materials may be washed with the above inert medium before the next contact with the alkoxy compound and titanium alkoxide, but better results will be obtained if the next contact is carried out in the same system. It is preferable.

(2) Contact with the alkoxy compound and titanium alkoxide The contact product obtained in [1] above and the alkoxy compound (C
The contact with component) and titanium alkoxide (component D) is achieved by first contacting component C and then contacting component D, or by contacting component C and component D simultaneously.

The contact between the contact material and the components C and D is desirably carried out in the presence of the above-mentioned inert medium.

The contact temperature and contact time are the same as in the case of [1] above, but it is also possible to adopt a method in which the contact is first carried out at a low temperature and then the temperature is raised to continue the contact.

The amount of component C used is 0.01" in molar ratio to component A.
~10, and 0.1 to 10 for the B component.

Also, the amount of component D used is 0.0 molar ratio to component C.
1 to 0.5, preferably 0.02 to 0.1.

The solid obtained as described above (solid ■) may be washed with a suitable detergent, for example the inert medium mentioned above, and, if necessary, dried, before the next contact with the refiner. It's okay.

(3) Contact with olefin Contact with olefin is carried out in the presence of the organoaluminum compound described above. Contact with the olefin (hereinafter referred to as prepolymerization) is preferably carried out in an inert hydrocarbon. Inert hydrocarbons include propane, butane, pentane, hexane, heptane, octane, decane, kerosene,
Examples include aliphatic, alicyclic or aromatic hydrocarbons such as cyclohexane, benzene, toluene, and xylene.

When prepolymerization is carried out in an inert hydrocarbon, 0.01 to 500 g of solid I per 11 of said hydrocarbons, especially 0.1 to
It is desirable to set it as 50g. The organic aluminum compound has an aluminum/titanium (atomic ratio) of 0.01 to 500.
, in particular, from 0.5 to 100. The prepolymerization temperature is usually 60°C or lower, preferably 0°C to +50°C. Prepolymerization is usually carried out at normal pressure, but may be carried out under increased pressure if necessary. Further, the reaction may be carried out in the presence of a molecular weight regulator such as hydrogen.

Further, other olefins may be coexisting as long as the proportion is 5 mol% or less.

Prepolymerization is carried out in the presence of an organoaluminum compound, but an electron-donating compound may be used in combination with the organoaluminum compound. As the electron-donating compound, any of the above-mentioned electron-donating compounds used in preparing the catalyst component of the present invention can be used, but other electron-donating compounds such as organic silicon compounds, nitrogen, Electron-donating compounds containing heteroatoms such as sulfur, oxygen, phosphorous, etc. can also be used.

Specific examples of organosilicon compounds include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, tetraphenoxysilane, tetra(p-methylphenoxy)silane, tetrabenzyloxysilane, methyltrimethoxysilane, and methyl. Triethoxysilane, methyltributoxysilane, methyltriphenoxysilane, ethyltriethoxysilane, ethyltriisobutoxysilane, ethyltriphenoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltributoxysilane, butyltriphenoxysilane Sisilane, isobutyltriisobutoxysilane, bityltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, penzeltriphenoxysilane, methyltriallyloxysilane, dimethyldimethoxysilane, dimethyljethoxy Silane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldihexyloxysilane, dimethyldiphenoxysilane, diethyljethoxysilane, diethyldiisobutoxysilane, diethyldiphenoxysilane, dibutyldiisopropoxysilane, dibutyldibutoxysilane, cyphthyldiphenoxysilane, diisobutyljethoxysilane, diisobutyldiisobutoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane, diphenyldibutoxysilane,
Examples include dibenzyljethoxysilane, divinyldiphenoxysilane, diallyldipropoxysilane, diphenyldiallyloxysilane, methylphenyldimethoxysilane, and chlorophenyldiethoxysilane.

Specific examples of electron-donating compounds containing a petero atom include:
Compounds containing a nitrogen atom include 2.2.6.6-titramethylpiperidine, 2,6-dimethylpiperidine, 2.
6-diethylpyrrolidine, 2,6-diisopropylpyrrolidine, 2,2,5,5-tetramethylpyrrolidine, 2
゜5-Dimethylpyrrolidine, 2.5-diethylpyrrolidine, 2.5-diisopropylpyrrolidine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 1
．． 2.4-) dimethylpiperidine, 2.5-dimethylpiperidine, methyl nicotinate, ethyl nicotinate, nicotinamide, benzoic acid amide, 2-methylpyrrole,
2.5-dimethylpyrrole, imidazole, toluic acid amide, benzonitrile, acetonitrile, aniline,
paratoluidine, orthotoluidine, metatoluidine,
triethylamine, diethylamine, dibutylamine,
Tetramethylenediamine, tributylamine, etc. are compounds containing sulfur atoms such as thiophenol, thiophene, ethyl 2-thiophenecarboxylate, ethyl 3-thiophenecarboxylate, 2-methylthiophene, methylmercaptan, ethylmercaptan, isopropylmercaptan, butyl Mercaptan, diethylthioether, diphenylthioether, methyl benzenesulfonate,
Examples of compounds containing oxygen atoms such as methyl sulfide and ethyl sulfide include tetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2-ethyltetrahydrofuran, dioxane, dimethyl ether, diethyl ether, dibutyl ether, diisoamyl ether, diphenyl ether, anisole, Acetophenone, acetone, methyl ethyl ketone, acetylacetone, ethyl 2-furalate, isoamyl 2-furalate, methyl 2-furalate, propyl 2-furalate, etc., as compounds containing a phosphorus atom, include triphenylphosphine, tributylphosphine, triphenyl Examples include phosphite, tribenzyl phosphite, diethyl phosphate, diphenyl phosphate and the like. When an electron donating compound is used in combination with an organoaluminum compound, the ratio of aluminum (gram atom)/electron donating compound (gram mole) is 0.1 to 100, particularly 0.5 to 50.

By doing so, polyolefins are formed there and incorporated into solid I. In the prepolymerization, the content of polyolefin in solid I is 0.05 to 1 per 11 g of solid.
00g, preferably 0.1-50g1 especially 0.2-20
It is desirable to make it so that g.

The polyolefin-containing solid obtained as above is
Next, it is contacted with a halogen-containing alcohol, but prior to contacting with the alcohol, it can be washed with an inert carbonized fluid such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc., if necessary, and further Can be dried if necessary.

(4) Contact with halogen-containing alcohol The polyolefin-containing solid obtained in the above (3) may be brought into contact with the halogen-containing alcohol (component E) by mixing and stirring in the presence of an inert medium.

Inert media include pentane, hexane, heptane,
Hydrocarbons such as octane, decane, cyclohexane, benzene, toluene, xylene, 1,2-dichloroethane,
1.2-dichloropropane, carbon tetrachloride, butyl chloride,
Norogenated hydrocarbons such as isoamyl chloride, bromobenzene, chlorotoluene, etc. can be used.

The contact between the two is usually between -20°C and +150°C with a temperature of 0.1 to 1
It will be held for 00 hours. If the contact is accompanied by heat generation, a method may be adopted in which the two are first brought into contact gradually at a low temperature, and then the temperature is raised after the entire amount has been mixed, and the contact is continued.

Component E is, per gram atom of magnesium in the solid,
Usually 0.05 to 20 gmol, preferably 0.1 to 1
It is 0 grams mole.

The solid product obtained by catalyzing the solid and component E is subjected to the next contact, but if necessary, it may be washed with the above-mentioned inert medium prior to the contact.

(5) Contact with the electron-donating compound and titanium compound The contact between the solid product and the electron-donating compound (component F) and the titanium compound (component G) is as follows:
A method in which the solid product is brought into contact with the G component and then brought into contact with the F component; ■ A method in which the F acid component and the G component are simultaneously used to form the solid product. A method of contacting with a product can be adopted.

Each of the above-mentioned contacts is achieved by mixing and stirring in the presence or absence of an inert medium.

As inert medium it is possible to use the compounds mentioned above.

The contact between the solid product and the F component and the G component is usually 0 to 0.
It is carried out at 200°C for 0.5 to 20 hours.

The amount of component F used is 1% of magnesium in the solid product.
The amount per gram atom is 0.005 to 10 gram mol, preferably 0.01 to 1 gram mol. In addition, the G component is 0 per gram atom of magnesium in the solid product.
．． It is used in an amount of 1 gram mol or more, preferably 1 to 50 gram mol.

The catalysis of the solid product and the G component can be carried out two or more times. The contact method may be the same as above. If necessary, the previously contacted material may be washed with an inert medium, and the G component (and the medium) may be newly added thereto and brought into contact.

The catalyst component according to the present invention can be produced as described above, but if necessary, the catalyst component may be washed with a hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be further dried if necessary.

The catalyst components obtained in the present invention are group 1 to group Ⅰ of the periodic table.
In combination with organic compounds of group metals, it is used as a catalyst for homopolymerization of olefins or copolymerization with other olefins.

Organic compounds of Group I to Group II metals. Examples of the organic metal compounds include lithium, magnesium,
Organic compounds of calcium, zinc and aluminum can be used. Among these, organoaluminum compounds are particularly suitable. The organoaluminum compound that can be used may be any of the above-mentioned compounds used in preparing the catalyst component according to the present invention, but among them, trialkylaluminum is preferred, and triethylaluminum and triisobutylaluminum are particularly preferred.

Examples of organic compounds of metals other than aluminum include diethylmagnesium, ethylmagnesium chloride, diethylzinc, and other compounds such as LiA1(CJs)a and LiA1(CJ+s)a.

Further, the organometallic compound may be used alone or in combination with an electron-donating compound.

As the electron-donating compound, (5
) Any compound may be used as long as it is an electron-donating compound consisting of an organosilicon compound or an electron-donating compound containing a petero atom, which is sometimes used in combination with an organoaluminum compound in the F component used in (3).

Two or more types of these electron-donating compounds may be used. Further, these electron-donating compounds may be used when an organometallic compound is used in combination with a catalyst component, or may be used after being brought into contact with an organometallic compound in advance.

The amount of the organometallic compound used in the catalyst component according to the present invention is usually 1 to 1 per gram atom of titanium in the catalyst component.
2000 gmol, especially 20 to 500 gmol is preferred.

The ratio of the organometallic compound to the electron-donating compound is selected within the range of 1 to 40, preferably 1 to 25 gram atoms of the organometallic compound as aluminum per mole of the electron-donating compound.

Polymerization of olefins The catalyst component and organometallic compound obtained as above (
and electron-donating compounds) have a carbon number of 2 to 1.
It is useful as a catalyst for the homopolymerization of 0 monoolefins or the copolymerization with other olefins or diolefins having 3 to 10 carbon atoms, but especially α-olefins, especially α-olefins having 3 to 6 carbon atoms. - homopolymerization of olefins, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, etc. or mutual and/or
It also shows extremely excellent performance as a catalyst for random and block copolymerization with ethylene.

The polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, inert carbonization of normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually in the range of -80°C to +150°C, preferably 40 to 120°C. The polymerization pressure may be, for example, 1 to 60 atmospheres. The molecular weight of the resulting polymeric couple can also be controlled by the presence of hydrogen or other known molecular weight regulators. In addition, the amount of other olefin to be copolymerized with the olefin in the copolymerization is usually selected in the range of up to 30% by weight, particularly in the range of 0.3 to 15% by weight, based on the olefin. The polymerization reaction using the catalyst system according to the present invention may be carried out in a continuous or batchwise reaction, and the conditions may be those commonly used. Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages.

Effects of the Invention The catalyst component obtained in the present invention is effective as a catalyst component in the production of polyolefins, particularly isotactic polypropylene, random copolymers of ethylene and propylene, and block copolymers of ethylene and propylene. be.

The polymerization catalyst using the catalyst component according to the present invention has high polymerization activity and stereoregularity, and can maintain the high polymerization activity for a long time during polymerization, and the obtained olefin polymer powder has a low bulk density. expensive. This catalyst component exhibits only a slight decrease in polymerization activity even when stored for a long period of time, and since the polymerization activity is high, there is little catalyst residue in the polymer.

EXAMPLES Next, the present invention will be specifically explained using examples and application examples. However, the present invention is not limited only to the examples. In addition, the percentages shown in the examples and application examples
(%) depends on the model unless otherwise specified.

The heptane-insoluble content (hereinafter referred to as "old"), which indicates the proportion of crystalline polymer in the polymer, is the remaining amount when extracted with boiling n-hebutane for 6 hours using an improved Soxhlet extractor. Bulk density was measured according to ASTM-01895-69 Method A.

Example 1 Contact between silicon oxide and n-butylethylmagnesium A 200 mf flask equipped with a dropping funnel and a stirrer was purged with nitrogen gas. In this flask, add silicon oxide (
Manufactured by DAVISON, product name G-952, specific surface area 30
2 m2/g, pore volume 1.54 cm3/g, average pore radius 204 people) (hereinafter referred to as 5 in2) in a nitrogen stream. 00t: 5g baked for 8 hours
and n-hebutane were added.

Furthermore, a 20% n-hebutane solution of n-butylethylmagnesium (hereinafter referred to as OHM) (trade name: MAGALA BBM, manufactured by Texas Alkyls) 20rd (B
BM and L Te26.8 Mi! Add J%Jl/) and heat to 90°C.
The mixture was stirred for 2 hours.

Contact with tetraethoxysilane and tetraethoxytitanium After the above suspension was cooled to 0°C, an n-hebutane solution containing 13-l of tetraethoxysilane and 2rnl of tetraethoxytitanium was added dropwise from the dropping funnel over 30 minutes. did. After dropping, the temperature was raised to 50°C over 1.5 hours, and the temperature was increased to 50°C.
Stirring was continued for 1 hour at 0°C. After the reaction was completed, the supernatant was removed by decantation, and the resulting solid was washed with 70-n
- Washed with hebutane at room temperature, and further removed the supernatant by decantation. This washing treatment with n-hebutane was further performed twice to obtain a solid (solid A).

Prepolymerization: 3 g of the above solid A and 50 ml of n-hebutane! was placed in a 200 ml glass autoclave purged with nitrogen gas. After degassing the gas phase at room temperature, introduce ethylene gas. n
- Hebutane was saturated with ethylene. Next, a solution of diethylaluminum chloride in n-hebutane (1 as AI)
Ethylene polymerization was carried out by adding mol/A) 37.5-.

After continuing polymerization until the amount of polyethylene produced reached 3 g, the supply of ethylene gas was stopped. The solid phase part is 50-n
- A solid (Solid B) was prepared by washing with hexane five times at room temperature.

2.2.2-) 86 g of solid in contact with lychloroethanol
and n-hebutane 50- was replaced with nitrogen gas 2001
into a nl flask. 2.2.2-) 18 ml of n-hebutane solution containing 8 ml of chlorethanol was added dropwise over 30 minutes, and stirring was continued for 1 hour at room temperature. After washing with hebutane five times, a solid (Solid C) was obtained.

Contact with titanium tetrachloride and di-n-butyl phthalate 5 g of solid C and 42 ml of n-hebutane were replaced with nitrogen gas in advance for 200 mj! Then, 2.41 nl of titanium tetrachloride was added and heated to 80°C. Here,
9 mj of n-hebutane solution containing 0.5 ml of di-n-butyl phthalate! was added dropwise over 5 minutes, and contact was carried out at 80°C for 2 hours with stirring. 700mj each of n-heptane for the solid phase!
After washing twice at 70°C, titanium tetrachloride 24rn1
．． and 42rnIl of n-hebutane were added, and the mixture was heated at 70°C for 2 hours.

The solid phase portion was washed five times with 70 rnl of n-hebutane at room temperature each time and dried under reduced pressure for 1 hour to obtain 4.6 g of the catalyst component. This catalyst component contained 5.1% titanium and 51% polyethylene.

Example 2 A catalyst component was prepared in the same manner as in Example 1, except that washing with n-hexane after prepolymerization was not performed.

Comparative Example 1 In Example 1, tetraethoxytitanium was not used,
A catalyst component was obtained in the same manner as in Example 1, except that preliminary polymerization was not performed. This catalyst component was prepolymerized in the same manner as the prepolymerization in Example 1 to prepare a catalyst component.

Example 3 A catalyst was prepared in the same manner as in Example 1, except that a di-n-hexylmagnesium solution (trade name: MAGALADAHM, manufactured by Texas Alkyls) was used instead of the 88M solution used as organic Mg in Example 1. Prepared.

Example 4 A catalyst component was prepared in the same manner as in Example 1 except that triethoxyaluminum was used instead of the tetraethoxysilane used together with the alkoxy compound.

Example 5 A catalyst component was prepared in the same manner as in Example 1 except that tetra-n-butoxytitanium was used instead of the tetraethoxytitanium used as the titanium alkoxide.

Example 6 In Example 1, p-
A catalyst component was prepared in the same manner as in Example 1 except that chlorophenol was used.

Example 7 A catalyst component was prepared in the same manner as in Example 1 except that p-chlorophenol was used instead of di-n-butyl phthalate used as the electron donating compound.

Comparative Example 2 In Example 3, a catalyst component was prepared in the same manner as in Comparative Example 1.

Comparative Example 3 In Example 4, a catalyst component was prepared in the same manner as in Comparative Example 1.

Comparative Example 4 In Example 5, a catalyst component was prepared in the same manner as in Comparative Example 1.

Comparative Example 5 In Example 6, a catalyst component was prepared in the same manner as in Comparative Example 1.

Comparative Example 6 In Example 7, a catalyst component was prepared in the same manner as in Comparative Example 1.

Application Example 1 Polymerization of propylene In a 1.5β stainless steel autoclave equipped with a stirrer, 50 μ of the catalyst component obtained in Example 1 and 0.1 mol of triethylaluminum in 11 n-hebutane were placed in a nitrogen gas atmosphere. 4 ml of a solution containing phenyltriethoxysilane and 21r11 of a solution containing 0.04 mol of phenyltriethoxysilane in 1 liter of n-hebutane were mixed and held for 5 minutes. Next, 300 ml of hydrogen gas as a molecular weight control agent and 11 ml of liquid propylene were injected under pressure, and then the temperature of the reaction system was raised to 70° C., and propylene was polymerized for 1 hour.

After the polymerization is completed, unreacted propylene is purged and the old 96
．． 221 g of white polypropylene powder with a bulk density of 8% and a bulk density of 0.39 g/cm' was obtained. The catalyst residue in the polymer had a chlorine content of 28 ppm.

Further, the catalyst component obtained in Example 0.1 was placed in a glass container purged with nitrogen gas, sealed and kept at 40°C for 30 days and 60 days.
After being stored for a day, it was subjected to propylene polymerization. Polymerization of propylene was carried out in the same manner as above, and the results are shown in Table 1. From the description in Table 1, it can be seen that storage deterioration is slight.

Application Examples 2 to 13 Propylene was produced in the same manner as Application Example 1, except that the catalyst components obtained in Examples 2 to 7 and Comparative Examples 1 to 6 were used instead of the catalyst components obtained in Example 1. Polymerization was performed. The results are shown in Table 1.

Table 1 1 Example 1-28 96.8 0.3
9〃30 28 96.7 0,39 〃60 29 96.8 0.39 2 Example 2 - 31 96.5 0.3
8” 30 33 96.5 0J8〃60
34 96.3 0.38 3 Example 3 - 29 96.8 0.3
9” 30 29 96.7 0.39〃60
30 96.7 0.39 4 Example 4 - 33 96.6 0.3
9〃30 33 96.6 0.39 ” 60 34 9'6.6 0.395
Example 5 - 29 96.8 0,39〃3
0 30 96.8 0.38 6 Example 6' -3596,60,39〃30
37 96.5 0.39〃60
38 96.5 0.397 Example?
-' 37 94.8 0.39"
30 39 94.7 0J9”
60 40 94.7 0,39
8 Comparative example 1 - 29 96.8 0.3
9N 30 35 96J
OJ9〃 60 42 96J
01399 Comparative example 2-30 9
6.7 0J9〃30 34 96.7
0.38〃60 38 96.7 0J9
10 Comparative example 3 - 34 96.6 0
J9〃30 43 96.6 0.39"
60' 49 96.6
0.3911 Comparative example 4 - 30 96
．． 6 0J9” 30 34
96.5 0.39〃60 37 96.
6 0.3912 Comparative example 5-38
96.5 0,38〃30 45 96.
5 0J8〃60 51 96.5 0
．． 3813 Comparative Example 6-37 94.
7 0.39〃30 46 94.7 0
J9〃60 55 94.6 0.39

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a process for preparing a catalyst component of the present invention.

Claims (1)

[Scope of Claims] (a) After bringing the metal oxide and (b) dihydrocarbylmagnesium into contact, (c) a compound of the general formula X^1_nM(OR^1)_m_-_n [where X^1 is Hydrogen atom, halogen atom or hydrocarbon group having 1 to 20 carbon atoms, M is a boron, carbon, aluminum, silicon or phosphorus atom, R^1 is a hydrocarbon group having 1 to 20 carbon atoms, m is an atom of M value, m>n≧0. ] and (d) titanium alkoxide represented by the general formula Ti(OR^2)_4 [wherein R^2 represents a hydrocarbon group having 1 to 12 carbon atoms. ] in the presence of (e) an organoaluminum compound, (f) contact with an olefin, then (g) contact with a halogen-containing alcohol, and further (h)
A catalyst component for olefin polymerization that is brought into contact with an electron-donating compound and a (li)titanium compound.